Amino derivatives of glucopyranose polymers



Dec. 9, 1952 GAVER ETAL 2,621,174

AMINO DERIVATIVES OF GLUCOPYRANOSE POLYMERS Original Filed May 9, 1947 3Sheets-Sheet 1 Pi g l C cLrbolzgzlrflw H mi lager COTI'LPDLLTL (I IHeaizing 61C i Reaction, Proclu ctl FigZ carbohydraie flmicle Ham 5+1 CCarbohydrate Esi'er Fig.3

INVENTOR. ENNETH M. GAVER. JTHER P. LAJURE EVI M. THOMAS THEIR ATTORNEYDec. 9, 1952 K. M. GAVER ET AL AMINO DERIVATIVES OF GLUCOPYRANOSEPOLYMERS 3 Sheets-Sheet 2 Original Filed May 9, 1947 Figi'r C qrbolzg(1rd:

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HEIR ATTORNEY Dec. 9, 1952 K. M. GAVER EIAL ,6 ,174

AMINO DERIVATIVES OF GLUCOPYRANOSE POLYMERS Original Filed May 9, 1947Carbohg drde Unstable nfi'r'ogen containing carbohydraie 0. cl 11117 on.c om. Poun. J,

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I Hediing 81 c 6 iarc hamin e INVEN TOR. M. G H VER T HE IR. ATTORNEYPatented Dec. 9, 195 2 AMINO DERIVATIVES 0F GLUCOPYRANOSE POLYMERSKenneth M. Gaver, Columbus, Esther P. Lasure, Grove City, and Levi M.Thomas, Columbus, Ohio, assignors to The Keever Starch Company,Columbus, Ohio, a corporation of Ohio Original application May 9, 1947,Serial No. 747,108. Divided and this application June 16, 1950, SerialNo. 168,594

11 Claims.

This application is a division of our copending application Serial No.747,108, filed May 9, 1947, now Patent No. 2,538,903.

The inventions disclosed in this application relate to new compositionsof matter or compounds and to new processes for the formation of suchnew compounds. The processes described herein illustrating ourinventions are especially designed to produce new products fromcarbohydrates such as starch.

The process invented by us comprises in general the reaction of anamidogen compound with a starch or some other suitable carbohydrate in anonaqueous system at a temperature of 81 C. and higher. As used in thisspecification and claims we define amidogen compounds to mean compoundshaving the radical NHz which is known only in combination in amines,amides and their derivatives. The amidogen compound may thus be anamide, an amine or a compound containing either one or more amide oramine groups. In carrying out the process of the reaction of an amidogencompound with a carhohydrate, we produce many new compounds which wehave discovered and synthesized by our process.

For example, in carrying out certain preferred embodiments of ourprocesses'we produce certain specific new products which we havediscovered and synthesized by our processes, these products being in thenature of amido carbohydrate esters which we have designated by thecoined word carbohydramate; amido starches which we have designated bythe coined word starchamate; amino carbohydrate derivatives which wehave designated by the coined word "carbohydramine; and amino starchderivatives which we have designated by the coined word starchamine. Wedefine these words as follows for the purposes of their use in thisspecific.- tion and in the claims hereof: Carbohydramate means acompound having an amido-containing group substituted for one of thehydrogen atoms of each of one or more of the several hydroxyl groups ofthe carbohydrate molecules so as to form an amido ester. The wordstarchamate means a compound composed of an undetermined number ofpolymerized glucopyranose units wherein one or more amido-containinggroups or radicals are substituted for the hydrogen atoms of one or moreof each of the several hydroxyl groups of the starch unit so as to forma polymerized compound which in fact is an Carbohydramine means aamino-containing group substituted for one of the hydrogen atoms of eachof one or more of the several hydroxyl groups of the carbohydratemolecules so as to form an amino derivative. The word starch amine meansa compound composed of an undetermined number of polymerizedglucopyranose units wherein one or more amino-containing groups orradicals are substituted for the hydrogen atoms of one or more of eachof the several hydroxyl groups of the starch unit so as to form apolymerized compound which is in fact a starch derivative.

Prior to our inventions disclosed herein, as is disclosed in a patentapplication of Kenneth M. Gaver, Esther P. Lasure and Derk V. 'IieszenSerial No. 357,995, now abandoned, and in the continuation thereofSerial No. 707,318, now Patent No. 2,518,135, methods of formingmonosodium starchates and other monoalkali starchates and monometallicand monoorganic derivatives thereof and the products of such methodswere known. Also, by the use of prior art methods, mono andpolysubstituted products of cellulose and of simple sugars have beenprepared as is described, for example, in Scherer and Hussey, Journal ofAmerican Chemical Society, 53: 2344; 1931; Schorigin et al., Berichte69; 1713 (1936); Peterson and Barry, U. S. Patent 2,157,083 (1939);Muskat, Journal of American Chemical Society, 561693 (1934); and Muskat,Journal of American Chemical Society, 5612449 (1934).

However, when we attempted to substitute amino and amido radicals in amanner similar to that in which alkali metal radicals were sub stituted(that is, by the reaction of starches and other carbohydrates withsimple ammonium hydroxide) and by the reaction of ammonia directly, orin a manner suggested by the prior art literature listed above, suchattempted substitutions were found to be impossible.

One of the objects of our invention is the provision of new and usefulprocesses of forming new and useful carbohydrates.

A further object of our invention is the provision of new and usefulprocesses for forming amino carbohydrate derivatives and amidocarbohydrate esters.

A further object of our invention is the provision of new and usefulprocesses of forming amido starch ester. compound having an various newproducts from starch.

A further object of our invention is the provision of new and usefulprocesses for forming various amino and amido starches.

A further object of our invention is the provision of new and usefulamino and amido carbohydrate products.

A further object of our invention is the formation of new and usefulamino and amido starches.

A further object of our invention is new processes of forming certainknown carbohydrate esters by the reaction of carbohydrates with amidogencompounds.

Further objects and features of our invention will be apparent from areading of the subjoined specification and claims when considered inconnection with the accompanying drawings showing processes illustratingcertain embodiments of our invention.

In the drawings:

Fig. 1 is a diagram il'iustratins a process of forming a reactionproduct from a carbohydrate and an organic amidogen compound;

Fig. 2 is a similar diagram illustrating ess of forming a carbohydrateester;

3 is a similar diagram illustrating a process of forming a starch ester;

Fig. 4 is a similar diagram illustrating a process of forming acarbohydramate;

Fig. 5 is a similar diagram illustrating a process of forming astarchamate;

Fig. 6 is a similar diagram illustrating a process of forming an ureastarchamate;

Fig. 7 is a similar diagram illustrating a process of forming anaddition product by the reaction of a carbohydrate and a monoamine;

Fig. 8 is a similar diagram illustrating a process of forming acarbohydramine; and

Fig. 9 is a similar diagram illustrating a process of forming astarchamine.

As stated above, we found that it was impossible to react simpleammonium hydroxide with starch in a manner similar to that which sodiumand potassium hydroxide reacted or to react ammonia directly withstarch. Moreover, we found. that it was impossible to substitute anamino or amido radical in an alkali metal starchate in place of thesodium or potassium group and thus form amino or amido starches. Theinventions disclosed herein are based upon the discovery that when acarbohydrate is reacted directly with an amine or an amide at atemperature of 81 C. or higher, with or without a solvent, with orwithout agitation, a reaction will occur which Will go practically tocompletion provided there is sufficient reactant present for this tooccur.

Such reaction products may be prepared using all sorts of starches,dextrins, dextran, cotton, linen, sugars, glucosides, jute, ramie,cellulose and inulin. All of the polyamyloses and other saccharides,natural, derived and synthetic, tested reacted similarly.

It has been found that any alcohol is suitable as solvent as isevidenced by the use of the following alcohols which we have found whichmay be use. as solvents in preparing such carbohydrate esters andderivatives provided certain other variables are sufficiently controlledas will be discussed later.

Allyl Iso-amyl n-Amyl Sec.-amyl 2L proc- Anisyl BenzhydrolBenzoylcarbinol Benzyl 2,3-butanediol n-Butyl Iso-butyl Sec.-butylTort-butyl Sea-butyl carbinol B-(p-Tert. butyl phenoxy) ethyl CaprylCeryl Cetyl 3-chloro-2-propenol-l Cinnamic Crotyl Cyclohexanol DecylDiacetone Diethyl carbinol Dimethyl benzyl carbinol Dimethyl ethynylcarbinol Dimethyl n-propyl carbinol Dimethyl isopropyl carbinolDi-n-propyl carbinol Di-iso-propyl carbinol Ethyl 2-ethyl butyl 2-ethylhexanol Furfuryl n-I-Ieptyl 11-Hexyl Sec.-hexyl Trimethylene glycolLauryl Methallyl Methyl Methyl amyl Methyl butyl carbinol o-Methylcyclohexanol m-Methyl cyclohexanol p-Methyl cyclohexanol Z-methylpentanol-l Methyl isopropyl carbinol n-Nonyl n-Octyl Octanol-2Phenyl-propyl Tert.-amyl n-Propyl Iso-propyl Tetrahydrofurfuryl Triethylcarbinol Triphenyl carbinol Ethylene glycol Ethylene glycol monomethylether Ethylene glycol monoethyl ether Ethylene glycol monobenzyl etherEthylene glycol monobutyl ether Diethylene glycol Diethylene glycolmonomethyl ether Glycerol Glycerol a-n-butyl ether Glycerolay-di-Hlfilihll ther GIYCGI'Ol-a'y-dl-Phl-ZIIYI ether Glycerol(it-monomethyl ether Hexamethylene glycol 2-methyl 2,4-pentanediolDiethylene glycol monoethyl ether Diethylene glycol monobenzyl etherDiethylene glycol monobutyl ether Di-propylene glycol Propylene glycolTriethylene glycol Substantially any organic solvent is suitable as isevidenced by the use of the following organic solvents which may also beused similarly:

Ketones may also be used similarly as is evidenced by the use of thefollowing:

Acetone Methyl butyl Acetophenone o-Methyl cyclohexanone Anisalacetonem-Methyl cyclohexanone Benzalacetone p-Methyl cyclohexanone BenzophenoneMethyl ethyl Benzoylacetone Methyl hexyl Diethyl I Methyl n-propylDiisopropyl Methyl iso-propyl Ethyl phenyl Ethyl undecyl and variousothers.

Methyl amyl Ethers may also be used similarly as is evidenced by the useof the following:

Allyl Chloromethyl Allyl ethyl Dichloromethyl n-Amyl Diethylene glycoldiethyl Iso-amyl Ethyl butyl Anethole Ethylene glycol dibenzyl AnisoleEthylene glycol diethyl Benzyl Ethyl Benzylmethyl Phenetole n-Butylbenzyl n-I-Iexyl n-Butyl n-Propyl n-Butyl phenyl Iso-propyl 1,4-dioxaneDi-n-propyl and various others.

Benzyl ethyl It is clear therefore that all non-aqueous solvents capableof dissolving the amine or amide to the extent necessary aresatisfactory. However, attempts to condense the reactants in a watersolution failed.

It must be understood, however, that all these solvents mentioned do nothave the same utility in the process. However, any solvent which willdissolve the amine or amide used even in small amounts, is a suitablevehicle in which to carry out the reaction. As the reactants in solutioncondense they go out of solution leaving the solvent available foradditional increments of the reactants.

As stated above the carbohydrates and the amidogen compounds will reacteither with or without a solvent but if a solvent is used, it must benon-aqueous. Therefore, generally the relation occurs in any non-aqueoussystem.

REACTANTS Every amide tested reacted as desired. A partial list ofreacting amides included:

6. Urea Guanidine Thiourea Cyanamide Ethyl urea Dicyandiamide Butyl ureaMelamine Ammeline Ammelide Amidines Diphenyl guanidine Guanylurea Phenylbiguanidine Hydrazides Acetamide Formamide Oxalamide Long chain amides(i. e. stearamide, palmitamide, etc.) react only slightly with the longchain polysaccharides such as starch but react freely with carbohydratesof lower molecular weight such as the simple sugars. When the reactingamide contained two free amido groups, the reaction product had at leastone free amido group. However, when the amide had only one amido groupsuch as formamide, acetamide, benzamide, cyanamide, ammelide, etc. thereaction product was not an amido ester but, on the contrary, was aformate, an acetate, a benzoate, cyanate, etc. Also, nearly everyprimary amine tested reacted as desired; however, separate and distinctreactions occurred. In view of the above, we have separated thereactants into five groups.

Group I includes those amides having only one amido group. As thetemperature rises to 81 C. a reaction occurs in which ammonia isevolved. The reaction product although not an amide is an ester of thecarbohydrate reacted.

Group II includes those amides having one amido group and also havinganother amido or amido derived group. As the temperature rises to 81 C.a reaction occurs in which ammonia is evolved. The reaction product hasat least one amido or amido derived group which is not attached directlyto the carbohydrate.

Group III includes mainly those low boiling amines containing but oneamino group and no other close functional group. This group of aminesapparently add only. No ammonia is evolved.

Group IV includes mainly those higher boiling amines containing one andonly one amino group and at least one other close functional group. Thisgroup of amines apparently adds first and as the temperature rises to 81C., a reaction occurs in which ammonia is evolved. The reaction productcontains no nitrogen and is not an ester.

Group V includes mainly those amines containing more than one aminogroup. This group of amines apparently add first and as the temperaturerises to 81 C'., a reaction occurs in which ammonia is evolved. Thereaction product has an amino group.

A partial list of reactants includes:

Group I Formamide Cyanamide Acetamide Ammelide Benzamide and similarlyacting materials.

Group II Melamine Butyl urea Diphenyl guanidine Ammeline Phenylbiguanidine Amidines Oxalamide Guanylurea Urea Hydrazides ThioureaGuanidine Ethyl urea Dicyandiamide and similarly acting materials.

7. Group III Mono-ethyl. amine N-butyl amine N-propyl amine andsimilarly reaction amines.

Group IV 2-amino-2-methyl 2-amino-1-butanol 1,3 -propanedio1-4-amino-2-butanoland similarly acting materials.

Group V and: similarly reaction amines.

TEMPERATURE A temperature of 80-81 C; appears to be critical. During thecondensation of reactants containing two or more amido groups, as soonasthe temperature reaches 80-81 C. the product suddenly agglomerates andsettles out of the reaction mixture. Simultaneously with theagglomeration of the product ammonia is evolved, one mole of ammonia foreach mole of reactant entering the carbohydrate unit or molecule. Duringthe reaction of monoamides such as acetamide, benzamide, cyanamide,formamide, etc., ammonia is-evolved at the same temperature but theproduct is an acetate, benzoate, cyanate, or formate, etc. and isnot anamide.

During the reaction of monoamines, the temperature of 80-81 C. is alsocritical. Using temperatures up to 115 C. gives no evidence of theformation of any derivative other than mono.

PRESSURE Since the. reaction of the amides in all cases and of theamines of Groups IV and V involve the evolution of ammonia and since theammonia has a greater volume than it had in combination in the reactant,the use of pressure in such reactions wouldinterfere with the reactionitself and-the use of pressure must be avoided. A vacuum can be utilizedif desired to drive the reaction. to completion. However, pressure isnecessary with the lower boiling amines of Group III (e. g. ethylamine)so that the temperature requirements might be fulfilled.

AGITATION In the reactionswe are describing as soon as the reaction isinitiated the reaction product settles' from the reaction mixture as arubber-like mass. Usually this mass is so heavy it stops the agitator.However, the reaction apparently proceeds uninterruptedly. In the caseof reaction of amides without solvent the reaction mixture softens;ammonia is evolved and the mixture again hardens (cakes) and does notsoften again in this temperature range. At the softened stage theproduct is very sticky; afterwards, however, it is not sticky butpowdery. Better yields in a shorter reaction time could undoubtedly beobtained with eificient agitation but nothing, that we have as yetobserved, indicates that agitation is necessary.

TIME

No exact definition of the time effect canbe given. In repeatedpreparations We have been able to discern no differences between slowheating and rapid heating. Neither were we able to detect anydiiferences between laboratory and 8. pilotplant operations as farastime was concerned'.

MECHANISM- Where starch and other carbohydrates are treated with anamine. or amide at 81 C. and above, this reaction proceeds as accordingto the following equations in. which R may be hydrogen or anyorganic-radical and where R is an active functional groupas', forexample, a hydroxyl or a nitrogen group:

heat CtHmOs RQNCQN-Ha. CsH9Q OCNHg.+ NH) (See Example I.) 2.

heat 00111005 2R2NC ONE: CsHaOg-(O CNRg): ZNH: (See Example II.) 3.

heat CtHinO5-I- R(CONH2)2 r CGHQO5OCRCONHQ+NH2 (See Examples I, II, andIII.)

As illustrated in Fig. 1 a carbohydrate heated with an amidogen compound(an amide, amine) to a temperature of 81 C. gives a reaction product. Ifthe amidogen compound is an amide, ammonia (Fig. 2) is evolved and acarbohydrate ester is formed. If starch is the carbohydrate and isheated with an amide (Fig. 3), ammonia is evolved and a starch ester isformed. If thereactant is a monoamide, there is no amidogen group in theproduct. If the amidogen compound is a polyamideas; for example, adiamide, either a carbohydramate (Fig. 4) or a starchamate (Fig. 5) isformed, ammonia being evolved in each case. It follows that if starch issimilarly heated with urea (Fig. 6) a starchamate is formed withevolution of ammonia. If starch or other carbohydrate is heated with apolyamine (Figs. 8-and 9 a starchamine or carbohydramine is formed, withevolution of ammonia in each case.

If starch or other carbohydrate is heated with a monoamine, the reactionvaries. Insome cases, ammonia is evolved and the product contains nonitrogen. In other cases, no ammonia is evolved and the'product isanaddition product. This distinction may depend on the presence or absenceof another close active-functional group. If there is such other closeactive functional group, ammonia is usually evolved and the productcontains no nitrogen. Onthe other hand usually where there is no otherclose active functional group, no ammonia is evolved and the product isan addition product.

The difference in the reaction may be on account of the lower boilingpoints of the reactants in Group III. As stated above where the boilingpoint is relatively low, pressure is necessary to prevent evaporation ofthe amine. Such pressure probably prevents the evolution of ammonia andprevents the substitution for the hydrogen of the hydroxyl group of theglucose units.

We believe that in the reactions describedabove, the amines form onlymonosubstitution products. On the other hand, the amides (where there isa sufiicient quantity of the amide present as in Examples II and III)form di and tri amide e. g. urea starchamates. They form mono ureastarchamate where only the proper stoichiometric quantity is present. Webelieve that the products of Examples I and III are respectivelysubstantially pure mono and tri urea starchamates only but that possiblythe product of Example II may in certain cases contain relatively smallproportions of mono and tri urea starohamates as well as a largeproportion of di urea starchamate.

EXAMPLES Example I (Illustration of Equations 1 and 7 above) 100 lbs. ofcorn starch 35 lbs. of urea 50 gallons of toluene Heat with agitationand slow distillation until about gallons of distillate have beencollected. Filter on centrifuge, wash with toluene and dry in a rotaryvacuum dryer at a temperature below 160 C. The dried product weighs 111lbs. and contains 6.75% nitrogen (calculated 6.83%). Distillate containsammonia.

Example II (Illustration of Equation 2 above) 100 lbs. of rice starch 70lbs. of urea 50 gallons of toluene Heat with agitation and slowdistillation until about 10 gallons of distillate have been collected.Filter on a centrifuge, wash with toluene and dry in a rotary vacuumdryer at a temperature below 150 C. The dried product weighs 150 lbs.and contains 11.5% nitrogen (calculated 11.3%). Distillate containsammonia.

Example III (Illustration of Equation 3 above) 100 grams of wheat starch105 grams of urea (excess) 1000 ml. of toluene Heat with agitation andslow distillation until 250 ml. distillate have been collected. Filteron suction, wash with toluene and then with ether and then air dry.Ammonia is evolved in this reaction. This product solvates at thereaction temperature but may easily be desolvated with ethyl ether. Theair dried product weighs 177 grams and contains 14.1% nitrogen(calculated 14.4%).

Example IV (Illustration of Equation 4 above) 50 grams of corn starch 50grams of diethylene triamine 500 ml. toluene Example V (Illustration ofEquation 5 above) 16 grams of corn starch 50 ml. monoethyl amine Thestarch is dissolved in the monoethyl amine and is heated withoutagitation and without distillation under pressure 1'75# at a temperatureof C. for one hour. Cool, let the excess ethyl amine evaporate off.Weight of reaction product 21 grams. This product then slowly losesethyl amine until the weight drops to that of the original starch.

Example VI (Illustration of Equation 6 above) 50 grams of corn starch 35grams of acetamide 500 ml. of toluene Heat with agitation and slowdistillation until about 250 ml. distillate have been collected. Filteron suction, wash with toluene and thenwith ether and then air dry. Theair dried product weighs 75 grams. Saponification of the air dry productand its air dry weight indicated the formation of the monoacetate.Ammonia was evolved in the reaction.

Example VII 50 grams of sucrose 17.5 grams of urea 500 ml. of tolueneThe materials were heated with agitation and slowly distilled until 250ml. distillate have been collected. The reaction product separated as :asirupy mass at the bottom of the reaction flask and no product weightcould be obtained. The product was cold water soluble, nitrogenous incharacter and extremely hygroscopic.

Example VIII 50 grams of dry thin boiling corn starch 22 grams of ethylurea (contains 20% free urea) 500 ml. of toluene 50 grams of dry ricestarch 500 ml. of toluene 30 grams of thiourea The materials were heatedwith agitation and slowly distilled until 250 ml. of distillate had beenExample X 50 grams of dry amioca starch 500 ml. of toluene 25 ml. offormamide The materials were distilled with vigorous agitation until 250ml. of distillate have been Example XI 5.0 grams of thin boilingWheat'starch 500 ml. of toluene 50 ml. of tetraethylene pentamine Thesewere mixed together in an open beaker and heated on a steam bath at 100C. until half the toluene had evaporated. The remaining toluene wasdecanted from the sirupy product and the product granulated with etherand filtered and air dried. The product weighed'79.5grams (calculated 83grams) and was very hygroscopic.

Example XII 100 grams air dry corn dextrin (81 grams dry weight) 100 ml.ethylene diamine 500 mlsbutanol and giving a very-flexiblefilm. Nitrogencontent 5.96% (calculated 6.3%

PRODUCTS The products of the reactions illustrated in Examples I, II andIII (Equations 1, 2 and 3) are pale yellow granular materials. Theyswell considerably in cold water and disperse in hot water to giveviscous sols but are insoluble in other solvents. Aqueous dispersionsdry to give brilliantly clear, tough, elastic films. The'prodnotof'Example I softens indefinitely around 160 C. The product of ExampleII softens indefinitely around 140 C. The product of Example III softensindefinitely around 120 C.

The products of the reaction illustrated in Example IV (Equation 4) arelikewise white to yellowish powders when dry. Many of the productssoften at relatively low temperatures and grinding of the product, isalmost an impossibility. The products are more or less highly hydratedin water. These reaction products are very stable derivatives.

At the completion of the reaction, the products of the reactionillustrated in Example V (Equation 5) are generally highly solvated.They are white to yellowish powders when dry and the-dry powders aremoreor less highly hydrated in water to give a product resembling alkalistarch paste. Generally speaking, these reaction products of the simpleprimary amines are not particularly stable to exposure to air. Theydecompose spontaneously in air as follows:

Starch NH2R Starch+RNHz The products of the reaction illustrated inExample VI has all of the properties expected of a monoacetate. It is awhite granular material, insoluble in cold water but is dispersed in hotwater. It is insoluble in other solvents.

12 POSSIBLE USES l. Intermediates in organic synthesis.

2. Intermediates in the manufacture of plastics.

3. Sizing materials for natural and synthetic fibers.

4. Thickeners for aqueous dispersions.

5. Emulsifiers, stabilizers, carriers and stiffening agents.

6. Binders and adhesives from aqueous dispersions.

7. Plasticizers'for ceramic manufacture.

8. Coating materials where smooth flexible films are required.

9. Filming materials for cold water paints.

. Ingredients in special dietary foods for ruminants.

Absorbent for pyrotechnic compositions.

Detergent for special soap compositions.

While the forms of embodiments of the present invention as hereindisclosed constitute preferred forms, it is to be understood that otherforms might be adopted, all coming within the scope of the claims whichfollow:

We claim:

1. The method of forming an amino derivative which comprises the step ofreacting starch with diethylene triamine at a temperature in the rangeof from C. to C. in a nonaqueous system wherein there is provided anonaqueous solvent having a boiling point at atmosperic pressure higherthan 80 C.

2. The process of treating starch which. comprises the step of mixingstarch with an amine at a temperature during the reaction period inaqueous system wherein there is provided a nonaqueous solvent having aboiling point at atmospheric pressure higher than 80 C.

3. The process of forming an amino starch derivative which comprises thestep of reacting starch with an amine having at least two amino groupsat a temperaturein the range of from 80 C. to 115 C. in a nonaqueoussystem wherein there is provided a nonaqueous solvent having a boilingpoint at atmospheric pressure higher than 80 C.

4. A process of forming a starch addition product which comprises thestep of mixing starch with an amine having only one amino group at atemperature in the range of from 80 C. to 115 C. in a nonaqueous systemwherein there is provided a nonaqueous solvent having a boiling point atatmospheric pressure higher than 80 C.

5. The process of forming glucopyranose polymer products which comprisesthe steps of mixing glucopyranose polymers with an amino compoundselected from the class consisting of ethylene diamine, phenyl diamine,propylene diamine, and the polymers of ethlyene which have not more thanfive free amino groups, and heating to a temperature in the range offrom 80 C. to 115 C. in .anonaqueous system wherein there is provided anonaqueoussolvent having a boiling point at atmospheric pressure higherthan 80 C.

6. The process of forming glucopyranose pol ymers which comprises thestep of mixing glucopyranose polymers with an amino compound selectedfrom the class consisting of ethylene diamine, phenylene diamine,propylene diamine, and the polymers of ethylene diamine which have notmore than five free carbon 13 atoms in a non-aqueous system at atemperature in the range of from 80 C. to 115 C.

7. The process of forming glucopyranose polymer products which comprisesthe step of mixing glucopyra-nose polymers with an amino compoundselected from the class consisting of ethylene diamine, phenylenediamine, propylene diamine, and the polymers of ethylene diamine whichhave not more than five free amino groups in a non-aqueous system at atemperature in the range of from 80 C. to 115 C. in substantiallystoichiometric quantities so that one amino group of each poly aminomolecule may react with a separate unit of the glucopyranose polymers.

8. The process of forming a starch reaction product which consists ofthe step of mixing an amino compound selected from the class consistingof ethylene diamine, phenylene diamine, propylene diamine, and thepolymers of ethylene diamine which have not more than five free aminogroups with starch in a nonaqueous system at a temperature of at least80 C. and not more than 115 C.

9. The process of forming a starch product which comprises the step ofmixing starch with ethylene diamine in a nonaqueous system at atemperature of from 80 C. to 115 C. to react the ethylene diamine withstarch to form a 2 amino derivative of starch.

10. Uniformly substituted glucopyranose polymer in which the glucoseunits have a formula Bio-- where R is a constituent selected from theclass consisting of lower aliphatic radicals having from one to eightcarbon atoms, lower aliphatic amino radicals having from one to threeamino groups, and phenylene.

11. A uniformly substituted starchate in which each of the glucose unitsof the substituted starchate has a formula of )(CHOR(NHz))bH0- where Ris a constituent selected from the group consisting of lower aliphaticradicals having from one to eight carbon atoms, lower aliphatic aminoradicals having from one to three amino groups and phenylene.

KENNETH M. GAVER. ESTHER P. LASURE. LEVI M. THOMAS.

REFERENCES CITED The following references are of record in the file orthis patent:

UNITED STATES PATENTS

2. THE PROCESS OF TREATING STARCH WHICH COMPRISES THE STEP OF MIXINGSTARCH WITH AN AMINE AT A TEMPERATURE DURING THE REACTION PERIOD INAQUEOUS SYSTEM WHEREIN THERE IS PROVIDED A NONAQUEOUS SOLVENT HAVING ABOILING POINT AT ATMOSPHERIC PRESSURE HIGHER THAN 80* C.
 7. THE PROCESSOF FORMING GLUCOPYRANOSE POLYMER PRODUCTS WHICH COMPRISES THE STEP OFMIXING GLUCOPYRANOSE POLYMERS WITH AN AMINO COMPOUND SELECTED FROM THECLASS CONSISTING OF ETHYLENE DIAMINE, PHENYLENE DIAMINE, PROPYLENEDIAMINE, AND THEPOLYMERS OF ETHYLENE DIAMINE WHICH HAVE NOT MORE THANFIVE FREE AMINO GROUPS IN A NON-AQUEOUS SYSTEM AT A TEMPRATURE IN THERANGE OF FROM 80* C. TO 115* C. IN SUBSTANTIALLY STOICHIOMETRICQUANTITIES SO THAT ONE AMINO GROUP OF EACH POLY AMINO MOLECULE MAY REACTWITH A SEPARATE UNIT OF THE GLUCOPYRANOSE POLYMERS.